CN102326260A - Copper delafossite transparent P-type semiconductor: methods of manufacture and applications - Google Patents

Copper delafossite transparent P-type semiconductor: methods of manufacture and applications Download PDF

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CN102326260A
CN102326260A CN2009801570495A CN200980157049A CN102326260A CN 102326260 A CN102326260 A CN 102326260A CN 2009801570495 A CN2009801570495 A CN 2009801570495A CN 200980157049 A CN200980157049 A CN 200980157049A CN 102326260 A CN102326260 A CN 102326260A
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cubo
semiconductor material
particle
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考施·K·辛格
奥姆卡拉姆·诺拉马苏
尼蒂·M·克里希纳
迈克尔·斯努尔
阿什托西·缇瓦瑞
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Applied Materials Inc
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • C—CHEMISTRY; METALLURGY
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    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

Methods for fabrication of copper delafossite materials include a low temperature sol-gel process for synthesizing CuBO2 powders, and a pulsed laser deposition (PLD) process for forming thin films of CuBO2, using targets made of the CuBO2 powders. The CuBO2 thin films are optically transparent p-type semiconductor oxide thin films. Devices with CuBO2 thin films include p-type transparent thin film transistors (TTFT) comprising thin film CuBO2. as a channel layer and thin film solar cells with CuBO2 p-layers. Solid state dye sensitized solar cells (SS- DSSC) comprising CuBO2 in various forms, including 'core-shell' and 'nano-couple' particles, and methods of manufacture, are also described.

Description

The manufacturing approach and the application of the transparent P type semiconductor of delafossite copper
Invention field
The present invention relates to transparent P type semiconductor material; More specifically; The present invention relates to the method for the transparent P type semiconductor material of manufactured copper iron ore copper (copper delafossite) and comprise the device of said delafossite copper product, said device comprises solar cell and transparent film transistor.
Background of invention
Transparent conductive oxide (TCOs), as, the zinc oxide of doping, tin indium oxide (ITO) and indium oxide molybdenum are widely used as optically transparent conductive electrode.These oxides demonstrate high conductivity and optical transparence in visible spectrum.Yet these oxides are characterized by the n type material all, and therefore the use of these oxides is restricted.For the use with TCOs extends to the application such as solar cell, transparent transistors, transparent LED (LEDs), ultraviolet ray (UV) detector etc., optical clear conduction P-type material that need be compatible with existing n type TCOs.Also need to incorporate the transparent P type semiconductor material in the device with low-cost substrate into, said low-cost substrate possibly limit technological temperature.In addition, need be used to form the method and apparatus of these materials.
In recent years, DSSC (DSSCs) has been subjected to very big concern as the effective substitute of the cost of conventional solar cell.DSSCs is with many aspects and the similar technological work of photosynthesis, and green plants produces chemical energy through this photosynthesis from sunlight.The center of these batteries is a thick semi-conductor nano particles film (electrode), and said film is that the absorption of capturing optical organic dye molecule provides high surface area.Light in the visible region of dye molecule absorption electromagnetic spectrum, and subsequently with the nano-structured semi-conducting electrode of electronics " injection ".This technology is attended by the transfer to dyestuff of electron donor amboceptor that electric charge supplies from electrolyte, and then resets circulation.Based on the DSSCs of liquid electrolyte at AM 1.5 (1000W m -2) shine upon the efficient that is issued to up to 11%.Yet the subject matter of these DSSCs is that liquid electrolyte is from the evaporation of battery and possible seepage.This has limited the stability of these batteries, and also causes DSSC technology scale-up serious problems in practical application.
At present, make solid-state DSSCs (SS-DSSCs) with greatly making great efforts to concentrate on through substituting liquid electrolyte with solid electrolyte such as fused salt, organic hole transferring material and polymer dielectric.Yet great majority suffer the problems of a large amount of transmission restriction of short circuit and ion among the SS-DSSCs, and therefore SS-DSSCs compares with the liquid version and has low conversion efficiency.Need: be used to make solid electrolyte material stable, high efficiency SS-DSSCs; Be used to make the handling implement of said solid electrolyte material; Comprise the new design of the SS-DSSCs of said solid electrolyte material; But and the manufacturing approach that is used to make said material and said SS-DSSCs.
Summary of the invention
Embodiments of the invention comprise the method, the equipment that is used for said manufacturing that are used for manufactured copper iron ore Cu material, comprise the device of said material and make the method for said device.
Some embodiment of the present invention is the technology that is used for manufactured copper iron ore Cu material, and said technology comprises: a synthetic CuBO 2The low-temperature sol-gel technology of material; One through control particle diameter control CuBO 2The technology of the band gap of material; One manufacturing can penetrate a dyeing porous TiO 2The CuBO of net 2The technology of superfines; One forms TiO 2-CuBO 2The technology of " core-shell " nano particle; One forms TiO 2-CuBO 2The technology of " nanometer coupling "; Reach one and form CuBO 2The technology of film is like pulsed laser deposition (PLD).For example, according to some embodiments of the invention, the method for manufactured copper boron oxide compound film comprises on substrate: through low-temperature sol-gel explained hereafter copper boron oxide powder; Compress said copper boron oxide powder to form target; And use said target on substrate, to form copper boron oxide compound film with film deposition tool, said film deposition tool is the pulsed laser deposition instrument for example.
Some embodiment of the present invention is used to make CuBO 2The equipment of material, said equipment comprise a nanometer powder production system.
Some embodiment of the present invention is the device that comprises delafossite Cu material, and said device comprises: one comprises CuBO 2Film is as the transparent film transistor of channel layer; Comprise film CuBO 2P-i-n and p-n solar cell as the p layer; And comprise the CuBO that takes various forms 2Solid-state dye sensitized solar cell (SS-DSSCs), said form comprises that " core-shell " reaches " nanometer coupling " particle.In some embodiments of the invention, SS-DSSC comprises: have CuBO 2General composition and stoichiometric p type, semiconductor material; The n type, semiconductor material; Dyestuff; With a pair of electrode; The first is optically transparent at least in the wherein said a pair of electrode, and wherein said n type, semiconductor material, said p type, semiconductor material and said dyestuff are between said a pair of electrode.
Some embodiment of the present invention is the method that is used to make the device that contains delafossite Cu, and said method comprises: through with ultra-fine CuBO 2Powder impregnation one dyeing porous TiO 2Net is made a SS-DSSC; Use a sol-gel technique with CuBO 2Particle is deposited into a TiO 2Make a SS-DSSC in the hole of net; Through the preparation embedding TiO is arranged 2One porous C uBO of particle 2Net is made a SS-DSSC; Through using TiO 2-CuBO 2" core-shell " nano particle is made a SS-DSSC; And through using TiO 2-CuBO 2" nanometer coupling " made a SS-DSSC.
Brief Description Of Drawings
To those skilled in the art, in conjunction with the accompanying drawings after the following description of reading specific embodiment of the present invention, these and others of the present invention and feature will become apparent, in the accompanying drawing:
Fig. 1 is the CuBO of diagram according to the embodiment of the invention 2The schematic flow diagram of sol-gel technology;
Fig. 2 is for showing CuBO 2Indirect band gap with the chart of the variation of particle diameter;
Fig. 3 is the sketch map according to the equipment that is used for nanometer powder production of the embodiment of the invention;
Fig. 4 is the schematic cross section according to the unijunction p-i-n solar cell with delafossite copper p layer of the embodiment of the invention;
Fig. 5 is the schematic cross section according to the many knot p-i-n solar cells with delafossite copper p layer of the embodiment of the invention;
Fig. 6 is the schematic cross section according to the p-n solar cell that in the p layer, has delafossite copper layer of the embodiment of the invention;
Fig. 7 is the CuBO according to the embodiment of the invention 2The schematic cross section of transparent film transistor (TTFT); And
Fig. 8 is the CuBO according to the embodiment of the invention 2The scanning electron micrograph of TTFT.
Fig. 9 is CuBO 2Instantaneous photoelectric current J PhAnd dark current J dTo the CuBO that makes according to the embodiment of the invention 2The chart of the electromotive force of particle;
Figure 10 is for showing TiO 2, ground state and excitation state the CuBO that makes according to the embodiment of the invention of ruthenium (Ru-535) dye well 2The sketch map on the ability rank of film;
Figure 11 is the sketch map according to the solid-state DSSC of the embodiment of the invention;
Figure 12 be measure from the DSSC that makes according to the embodiment of the invention, based on CuBO 2The chart of photoelectric current-voltage characteristic of DSSC, this chart has an illustration, this illustration illustrates as the conversion efficiency of this battery of the function of time (η);
Figure 13 A and Figure 13 B are for showing the CuBO with (A) large-size that is prepared by the method according to the embodiment of the invention 2The CuBO of particle, (B) nano-scale 2The mesopore TiO of powder 2The sketch map of film;
Figure 14 is used to prepare CuBO for showing according to the embodiment of the invention 2The chart of differential scanning calorimetry (DSC) of citrate gel;
Figure 15 A, Figure 15 B and Figure 15 C are sketch map, illustrate: (A) according to the embodiment of the invention fills mesopore TiO 2The citrate sol in the hole of film, (B) mesopore TiO 2Gel in the film reaches (C) TiO 2And CuBO 2The web of nano size particles;
Figure 16 is for having a nano-scale CuBO according to the embodiment of the invention 2The sketch map of the DSSC of the net of particle;
Figure 17 A and Figure 17 B are the TiO according to the embodiment of the invention 2-CuBO 2The sketch map of " core-shell " nano particle, wherein (A) shows with TiO 2As core and CuBO 2Show with CuBO as the particle of shell with (B) 2As core and TiO 2Particle as shell;
Figure 18 be according to the embodiment of the invention by TiO 2-CuBO 2The sketch map of the DSSC that " core-shell " particle is made;
Figure 19 is the TiO according to the embodiment of the invention 2With CuBO 2The sketch map of " nanometer coupling "; And
Figure 20 diagram is according to the TiO of the embodiment of the invention 2-CuBO 2The sketch map of related step in " nanometer coupling " synthetic.
Embodiment
To consult accompanying drawing at present and describe the present invention in detail, provide accompanying drawing as illustrative example of the present invention so that those skilled in the art can embodiment of the present invention.It should be noted that following each figure and instance are not to mean scope of the present invention is limited to single embodiment, through said or shown in some or other embodiment of whole exchange mode in the assembly also be possible.In addition; Can use under the situation that known elements partially or completely implements at some assembly of the present invention; Understand those parts essential to the invention in such known elements with only describing, and will omit the detailed description of other part in these known elements in order to avoid obscure the present invention.In this manual, should the embodiment that show single part be regarded as restriction; On the contrary, only if this paper has clearly regulation in addition, otherwise this invention is intended to contain other embodiment that comprises a plurality of same parts, and vice versa.In addition, the applicant is intended to any term in this specification or the claim is belonged to non-common or special implication, only if clearly according to setting forth like this.In addition, the present and in the future known equivalent of this paper through the mentioned known elements of the mode of explanation contained in the present invention.
The instance that this paper provides relates generally to CuBO 2Material; Yet many theories are applicable to other delafossite Cu material, for example, and CuAlO 2, CuGaO 2And CuInO 2In addition, the instance of the device that provides of this paper relates to solar cell device and transparent film transistor; Yet; In view of similar reason; Other device also can be benefited from and incorporate transparent P type semiconductive material into, said other device comprises transparent membrane photovoltaic device, transparent p-n diode, visible light and UV detector, be used to produce hydrogen photoelectrolysis device and be used for display and other device that low E glazing is used.Remove CuBO 2Outside, also can use AgBO 3, TlBO 3And Cu 1-xAg xBO 2The alloy of p type transparent semiconductor.Be used for synthetic CuBO 2The sol-gel technology of powder can be through improvement to be used for through solution deposition techniques (as: dip-coating, spraying, ink jet printing or spin coating) built up membrane.This sol-gel technology through improvement can be used as cryogenic technique with thin film deposition on multiple substrate, said substrate comprises pottery, monocrystalline and such as the responsive to temperature substrate of glass, metal forming and plastics.
Only if this paper has indication in addition, otherwise term copper boron oxide compound (copper boron oxide) and CuBO 2Interchangeable making is used to refer to optically transparent P type semiconductor material, and said material has CuBO 2And the general composition and the stoichiometry of delafossite crystal structure.
Be used for synthetic CuBO 2 The technology of powder and film
Developed via the synthetic CuBO of low temperature wet process 2The new technology of powder.Fig. 1 illustrates the schematic flow diagram of this treatment technology.In this technology, with CuO and B 2O 3Be dissolved in respectively in nitric acid and the water, and said two kinds of solution are combined to form homogeneous solution (110).In order to reach stoichiometric powder, the mol ratio of Cu and B is 1: 1.Be that 2: 1 mol ratio is added into this solution (120) with citric acid with citric acid and Cu subsequently.Citric acid is the chelating agent of tying with the metal ion key: copper atom of a citric acid molecule chelating and a boron atom.With this solution of deionized water dilution, make liquor capacity increase by 10 times (130) subsequently.Subsequently with this solution at 100 ℃ of about 18hrs. of refluxed (140).After refluxing, evaporate this solution to produce gel net (150).The temperature that this gel further is heated to 160 to 200 ℃ of scopes causes an exothermic reaction (burning), and produces CuBO 2Powder (160).Under the temperature of 300 to 500 ℃ of scopes, reacted powder is calcined about 2hrs. to remove any residual carbon.
The dilution of carrying out citric acid solution is in case the precipitated metal during the backflow.The reason of excessive citric acid is that citric acid fully is not dissociated into ion in solution, and when all Cu and B are chelated, can produce the film of better quality; Yet this must reduce to the minimum balance of carrying out with the excess carbon that during gel combustion, is formed by citric acid.In general, citric acid should surpass 1: 1 with the C ratio, and finds that about 2: 1 ratio provides gratifying result.
In addition, through the whole CuBO of control adjustable grain 2The band gap of particle.As stated, the delafossite copper powders may is synthetic by gel.Gained CuBO 2The particle diameter of powder is through changing the controlling reaction temperature of gel to solid.As stated, this is reflected under the environmental condition in 160 to 200 ℃ the scope and takes place.In order to reduce reaction temperature, reduce system pressure: the technology of this gel to solid is carried out through heating under vacuum.For example, the technology of this gel to solid is being carried out under 70 and 100 ℃ under the vacuum of 50Torr.So the color of synthetic powder is the indicant of technological temperature, that is, low technological temperature produces than small-particle and blue displacement color.For example, the powder color in 70 ℃ of formation under vacuum is blue, and the powder color in 160 ℃ of formation is a bronzing in air.In addition, the after annealing of powder or calcining cause particle diameter to increase and produce red displacement.At 500 ℃ of all powders of calcining down is bronzing, and this indicates similar particle diameter.The CuBO that produces at a lower temperature 2Powder samples shows high slightly band gap.Fig. 2 illustrates the CuBO as the function of average grain diameter 2The curve of indirect band gap.Along with average grain diameter is decreased to about 100nm from 200nm, indirect band gap increases to 2.6eV from 2.4eV.It should be noted that use above technology under vacuum in 70 ℃ of particles that form 200nm, and under environmental condition in 200 ℃ of particles that form 200nm.Use ultraviolet ray-visible spectrophotometer to measure indirect band gap.Use Scherrer ' s formula to measure particle diameter through X-ray diffraction, Scherrer ' s formula makes diffraction peak broadening relevant with crystalline size.It should be noted that along with particle diameter further reduces, band gap will continue to increase.
Use aforesaid nanometer powder through under 5MPa, pushing powder, under 20MPa, push the target that prepared one-inch in 20 minutes subsequently with counterpressure.Subsequently these are pushed in the vacuum chamber that target is placed on impulse laser deposition system.
In three kinds of organic solvents with acetone, isopropyl alcohol and the order ultrasonic clean substrate of methyl alcohol (like the glass of transparent conductive oxide coating) subsequently.In clean methanol, clean said substrate subsequently and with the air-dry drying of said substrate.Subsequently said substrate is installed on the substrate heater of impulse laser deposition system.To contain this vacuum chamber sealing of deposition targets and substrate and be evacuated to 1 * 10 -6The vacuum of Torr.In case reach 1 * 10 -6The pressure of Torr comes this target of In-Situ Cleaning through ablated surface.This cleaning procedure uses 2J/cm 2Laser energy, the laser pulse frequency of 10Hz and the target rotating speed of 18 °/s.For guaranteeing that removing all surface pollutes, through two omnidistance rotation ablation targets.After clean substrate, once more chamber is evacuated to 1 * 10 -6Torr, and with the speed of 10 ℃/min with substrate heating (to 500 ℃).Before deposition, substrate is remained in a constant temperature continue 10 minutes.Because therefore the low temperature requirement of the glass substrate of TCO coating uses the low deposition temperature.After 10 minutes, with high-purity O 2Gas is introduced in the chamber, and this chamber has the dividing potential drop in 1mTorr to 0.1Torr scope.In case this O 2Pressure reaches balance, then begins this depositing operation.Use has the KrF PRK ablation target in pulse duration of photon wavelength and the 25ns of 248nm.With 2J/cm 2Laser pulse frequency and the target rotating speed of 18 °/s of laser energy, 10Hz be used for deposition.These conditions produce the growth rate of
Figure BPA00001423097700061
/pulse.Film thickness is changed to from 80
Figure BPA00001423097700062
After deposition is accomplished, at O 2The film reduction that this substrate of cooling is deposited to prevent in the atmosphere.Do not hope the reduction of said delafossite copper film, because this can produce the decomposition of excess of oxygen room and said film.When reaching room temperature, shifting out also from this vacuum chamber film, vacuum stores to reduce pollution.
When using the substrate of anti-higher treatment temperature, depositing temperature can change in comprising the relative broad range of higher temperature.Under these situation, can press and optimize film character through change depositing temperature and oxygen at relative broad range.Hereinafter provides some instances.In alternate embodiment of the present invention, can use the substrate of sapphire, silicon or other anti-high treatment temperature.When with CuBO 2Be deposited on one of these high-temperature substrates last time, except that depositing temperature and oxygen pressure, this depositing operation is by carrying out with identical general step mentioned above.This depositing temperature and partial pressure of oxygen can reach 10 respectively between 350 and 700 ℃ -6With 10 -1Change between the Torr, to confirm the best growing condition.For example, for the CuBO on the silicon substrate 2Channel transistor is found to be respectively 550 ℃ and 10 -1It is desirable for device performance that the depositing temperature of Torr and oxygen are pressed.
Use the typical CuBO of above-mentioned deposition techniques 2Film is the nanocrystalline of about 20 nanometers of crystallite dimension.The optical transmittance of optical transmittance 200 to 900 nanometers under the wave-length coverage of this measurement exceeds 50%.According to estimates, direct band gap and indirect band gap value are respectively about 4.5eV and 2.4eV.Conductivity is through being measured as about 1.5Scm -1This material is the p type, has to be about 100cm according to estimates 2V -1s -1The charge carrier hall mobility.This material has CuBO 2And the general composition and the stoichiometry of delafossite crystal structure.
Said transparent semiconductive delafossite copper film can be used for multiple device, for example: transparent LED (LEDs), ultraviolet ray (UV) detector, solar cell, transparent transistors etc.Hereinafter provides some particular instances of device.
Yet, the CuBO that some application needs are minimum 2Particle, these particles are littler than the particle of common 200 nano-scales that produced by above-mentioned sol-gel technology.Design is also made the auxiliary manufacturing system of a laser to be used to prepare the CuBO of nano-scale 2Powder.Use this system, can fully limit and stable condition under continue to produce nano level powder.
Fig. 3 illustrates the schematic design figure of the auxiliary manufacturing system of this laser.The major part of evaporation chamber 210 is for continuing rotating circular disk 215, this rotating circular disk have along the edge of this rotating circular disk one contain material powder the circular passage.Laser beam 220 focuses on the powder surface of rotation and vaporize via an inlet tube.This technology is used to make CuBO with above-mentioned 2Nanometer crystal film (the PLD technology of crystallite dimension～20nm) is extremely similar.Yet, in the case, through inert gas is flowed consistently but not will directly be deposited on the material that will be somebody's turn to do through ablation on the substrate that keeps high temperature through the material (being the plasma form) of ablating and blow out the interaction area between laser emission and the powder target.Because the temperature between thermal evaporation zone and the surrounding atmosphere sharply changes, nucleation, condensation and cohesion are extremely fast carried out.This causes the formation of ultrafine particle.The constant flow of keeping inert gas is with the emerging drop of rapid dilution, and then makes and can not form hard coalescence through the edge fusion of drop.
During a revolution of disk, automatically recharge vaporized material by refill unit 230, and make the flattening surface of this filling by scraper.Thus, the powder surface feeding of cyclic regeneration to laser beam, and then is guaranteed stable and reproducible process conditions.Evaporation chamber 210 is connected to filtering chamber 240 via glass tube 245 systems with air tight manner.One extraction fan 250 is attached to filtering chamber 240 through flange, and this extraction fan 250 provides the constant flow of process gas, and this process gas is sucked into the evaporation region below.Through this air-flow, nano particle will be dragged in the filtering chamber 240, will on cylindrical paper 260 or metal bag filter, separate with aerosol at nano particle described in this filtering chamber.Any particle collection that inherent filtration device 260 is fallen is in nanometer powder container 270.Use this system to make the nano particle that diameter is about 20 ± 5 nanometers.This system can concentrate on the nano particle that the diameter of 5 to 500 nanometer range distributes in order to formation.As stated, consult Fig. 2, for for small-particle, CuBO 2The band gap of particle is bigger.
Has CuBO 2 The solar cell of P layer
Use aforesaid low temperature process, can p type copper boron oxide compound be incorporated into to the multiple solar cell of the transparent p layer of needs.For example, Fig. 4 is illustrated in the unijunction non-crystal silicon solar cell that has a transparent P type copper boron oxide compound p layer 330 on the transparency carrier.More detailed, the solar cell among Fig. 4 comprises glass/flexible base, board 310, transparency conducting layer 320 (like n type TCO film), p type copper boron oxide compound film 330, amorphous silicon absorber layer 340, n type amorphous silicon membrane 350 and back of the body contact 360.Back of the body contact 360 can be formed by aluminium (aluminium that for example, has 1% silicon or nickel).Copper boron oxide compound film 330 is thick between 8 and 100 nanometers usually.
Fig. 5 illustrates an instance of multijunction solar cell.Except that one the 2nd p-i-n storehouse, this multijunction solar cell is identical with the unijunction solar cell of Fig. 3.The top storehouse can have the differing absorption agent with the bottom storehouse, and for example, the i layer that is used for top storehouse 470 is a microcrystal silicon, and the i layer that is used for bottom storehouse 440 is an amorphous silicon.More detailed, the solar cell of Fig. 5 comprises: glass/flexible base, board 410; Transparency conducting layer 420 is such as n type TCO film; Include first storehouse of p type copper boron oxide compound film 430, i layer 440 and n layer 450; Include second storehouse and the back of the body contact 490 of p type copper boron oxide compound film 460, i layer 470 and n layer 480.Copper boron oxide compound film 430 and 460 thick between 8 and 100 nanometers.
Fig. 6 illustrates the solar cell with p layer 530, and this p layer comprises absorber material and p type delafossite copper film.This absorber material can comprise such as Cu-In selenide (CIS), CIGS thing (CIGS), Cu (In, Ga) (S, Se 2), CdTe, Cu 2ZnSnS 4Or the material of other II-V binary and ternary compound.This delafossite copper film can be between this absorbent and the conductive layer 520 or between this absorbent and cadmium sulfide n type layer 540.More detailed; The solar cell of Fig. 6 comprises glass/stainless steel/polymeric substrates 510, conductive layer 520 (like, molybdenum film), p layer 530, n layer 540 (like cadmium sulphide film), TCO/ resilient coating 550 (like the ITO/ Zinc oxide film), anti-reflection layer 560 (like the magnesium fluoride film) and hard contact 570.It should be noted that substrate 510 can be 1.5 millimeters thick usually.Molybdenum layer 520 is generally 0.5-1.5 micron thick and can be through sputtering sedimentation on this substrate.P layer 530 is generally the 1.5-2.0 micron thick, and absorber material can deposit through wet chemical processes; In the p layer, the delafossite copper film is generally 0.02 micron thick and can deposits through aforesaid laser ablation process.Cadmium sulfide n layer 540 is generally the 0.03-0.05 micron thick and can deposits through chemical bath deposition (CBD) technology.ITO/ zinc oxide film 550 is generally the 0.5-1.5 micron thick and can uses wet chemistry or radio frequency sputtering technology deposits.Magnesium fluoride anti-reflection layer 560 is generally 0.1 micron thick and can be through electron beam evaporation.Hard contact 570 can be processed by nickel/aluminium, this hard contact 570 visual these solar cell geometries and have a certain thickness in the 0.05-3.00 micrometer range, and can be through electron beam evaporation.
In addition, as discussed previously, the p type copper boron oxide compound in the solar cell instance that more than provides can be by other p type delafossite copper product (like, CuAlO 2, CuGaO 2And CuInO 2) substitute.In addition, for the purpose of the quantum efficiency that improves solar cell, this p type copper boron oxide compound film can be substituted by following two kinds of films: delafossite copper product film and such as second material membrane of p type amorphous silicon, p type microcrystal silicon or p type crystallite carborundum.
Has CuBO 2 The transparent film transistor of channel layer (TTFTs)
Transparent film transistor (TTFT ' s) becomes the actuating force that organic and flat-panel monitor were greatly paid close attention to and become to invisible microelectronics recently.All crystals duct member (grid, gate dielectric, drain electrode, source electrode and transparent oxide semiconductor channel layer) all can be processed by stable and transparent oxide material.Yet only n type oxide semiconductor TTFT ' s is obtained howling success by extensive proof.For great majority are used, need complementary p type TTFT ' s.CuBO 2For being used to make the feasible p molded breadth gap semiconductor of p type TTFTs.
Fig. 7 illustrates has p type CuBO 2The schematic cross section of the TTFT of passage 640.This TTFT comprises substrate 610, grid 620, gate insulator 630, p type CuBO 2Passage 640, source electrode 650 and drain 660.Substrate 610 can be glass or some other hard materials (like polymer).Grid 620 can be TCO, like ITO.Gate insulator 630 can be dielectric medium, like Al 2O 3, HfO 2, ZrO 2And rare earth oxide.Passage 640 is generally the 100-300 nanometer thickness.In the TTFTs of manufacturing, channel layer length changing between the 100 and 500 μ m width 0.5 and 5mm between change.CuBO 2Passage 640 can be deposited on the insulator layer 630 through pulsed laser deposition (PLD).Deposition parameter is identical with above-mentioned deposition parameter.Source contact 650 and drain contact 660 can be the thick metal level of 10nm (like platinum), perhaps be the thick transparent conductive oxide of 100nm (TCO) layer (as, the zinc oxide of ITO, adulterated al and the tin oxide of doped with fluorine).Drain contact 660 and source contact 650 sputter at the top of channel layer 640.
Fig. 8 illustrates the scanning electron micrograph such as single TTFT shown in Figure 7.Fig. 8 is the vertical view of device, wherein with grid 620, CuBO 2Passage 640, drain electrode 650 and source electrode 660 imagings.
CuBO 2The depositing temperature of passage 640 plays a part extremely crucial to device performance.Because limited resistance can allow to leak and then the infringement device performance via the electric current of dielectric layer, so in desirable field-effect transistor (FET), dielectric layer (gate insulator) has high resistance.For CuBO 2Passage TTFTs, the resistance between grid and the source electrode depends on CuBO sensitively 2Film deposition temperature.Depositing temperature is higher, and gate-source resistance is littler.The resistance of grid to source electrode reduces resistance owing to Cu and B element via the diffusion of dielectric layer to the dependence of temperature.Form CuBO owing to exist 2Required minimum heating power temperature, so resistance is not for selecting unique consideration of desirable depositing temperature.550 ℃ depositing temperature possibly be the desirable balance between these temperature requirements.Yet baseplate material can be limited to about 500 ℃ with depositing temperature.
In order to prevent to diffuse in the dielectric layer, can add diffusion barrier (not shown among Fig. 7) between 630 at passage 640 and dielectric layer (gate insulator) as the parasitic element of Cu and B.This diffusion barrier is the film that is deposited on the dielectric layer 630, CuBO 2Film (channel layer) 640 is formed at the top of this diffused barrier layer.That this diffusion barrier should be is thin, with dielectric material and CuBO 2Do not react and stop Cu or B to diffuse in the dielectric layer.Based on transition metal and rare earth oxide (as Ta 2O 5) or the diffusion barrier of transition metal and rare earth nitride (as TaN) maybe be for being fit to.The electric current that uses this kind resistance barrier can reduce via gate dielectric leaks.
In addition, as discussed previously, the p type copper boron oxide compound in the TTFTs instance that more than provides can be by other p type delafossite copper product (like CuAlO 2, CuGaO 2And CuInO 2) substitute.
Use CuBO 2 Solid-state dye sensitized solar cell
In order to can be used among the DSSCs; Require p N-type semiconductor N and dyestuff to have following character: (i) the p type material must be transparent in whole visible spectrum; Dyestuff is absorbing light (in other words, semiconductor must have large band gap) in visible spectrum, (ii) must have to can be used for the p type material is deposited on TiO 2Nanocrystal (n N-type semiconductor N) is gone up and is not dissolved or the method for degradation of dye individual layer, and (iii) dyestuff must make the excitation level of dyestuff be positioned at TiO 2Conduction band bottom on and the ground state level of dyestuff must be positioned under the valence band top edge of p type material.This condition is essential for the separation of guaranteeing the electron hole pair that light produces.
CuBO 2Can be based on TiO 2DSSCs in be used as the hole gatherer.In order to extract the hole from dyestuff, the valence band edge of material should be on the ground state level of this dyestuff.In order to judge CuBO 2Whether satisfy this condition, characterize through the execution Optical Electro-Chemistry and judge CuBO 2Flat rubber belting electromotive force and valence band edge.Use standard three electrode devices carry out electrochemistry and measure in 1M KOH solution (pH 12).Said three electrodes are CuBO 2Particle, large-scale platinum are to electrode and saturated calomel reference electrode (SCE), and all electromotive forces are all quoted said electrode.It should be noted that this CuBO 2Particle is the roundel through the following steps preparation: will use the CuBO through calcining of sol-gel technology by above-mentioned preparation with the single shaft hydraulic press 2In circular dyestuff, push; And further pass through 30, static pressure such as 000Psi are exerted pressure and were come this particle of closeization in 20 minutes.Wash this electrolyte constantly with pure nitrogen gas.Fig. 9 illustrates in the dark and the current-voltage curve under irradiation.As can from Fig. 9, find out photoelectric current (J Ph) appearance from electromotive force V ONFor+0.21V begins and along the cathode direction increase, this is the behavior of typical p type.Electromotive force V ONCan reasonably be regarded as electromotive force (V corresponding to the valence band location of material Fb).Use the known formula formula to estimate CuBO 2Valence band location:
E VB＝4.75+eV fb+0.059(pH-pH pzzp)
PH PzzpBe pH and discovery pH at 1 zeta potential (pzzp) point PzzpBe 8.2.Therefore, the result is illustrated in that valence band is positioned under the vacuum～5.2eV place (0.46eV is to SCE).
Figure 10 illustrates TiO 2{ R.Memming; " Solar energy conversion by photoelectrochemical processes "; Electrochemical Acta.25,77-88 (1980) }, ruthenium dye [suitable-two (isothiocyano) two (2,2 '-bipyridine-4; 4 '-dicarboxylic ester)-(it is called Ru-535 dyestuff { people such as Nazeeruddin, " Engineering of Efficient Panchromatic Sensitizers for Nanocrystalline TiO to ruthenium (II) hereinafter 2-based Solar Cells ", Journal of the American Chemical Society 123,1613-1624 (2001) }]) and the CuBO that processes as stated 2The energy diagram of particle.The excitation level of this dyestuff is positioned at TiO 2Conduction band on the 0.66eV place, and the ground state of this dyestuff is positioned at CuBO 2Valence band under the 0.39eV place.Clearly, said level of energy has satisfied the separation of charge condition of the electron hole pair of light generation admirably.Therefore, if in dyestuff, produce electron hole pair, then electronics will easily be injected into TiO 2Conduction band in, and the hole will easily be injected into CuBO 2Valence band.Figure 10 only illustrates the energy level of Ru-535 dyestuff; Yet some other dyestuffs of this energy level requirement can be advantageously satisfied in existence.This is described in greater detail in hereinafter.
Make a prototype DSSC and performance and the conversion efficiency of prototype DSSC are assessed.Figure 11 illustrates the sketch map of this battery.This battery is made by following.At first, through spray pyrolysis with TiO 2Thin solid film 720 (30-100nm is thick) is deposited on the glass plate 710 that is coated with electric conductive oxidation indium tin (ITO).After this with mesopore TiO 2Layer 730 is pressed into the TiO through spraying 2On the layer 720.For this reason, then use the titanium loudspeaker that impregnated in the suspension to carry out 10 minutes sonicated through stirring some hrs, with the TiO of 500mg 2Nanometer powder (diameter～5nm) be suspended in the 10mL straight alcohol.Use adhesive tape spacer layer (10um is thick) to make this slurries spread to ITO/TiO through the adhesive tape casting 2On the surface of substrate.Make the ethanol/TiO of gained 2Layer is dry in ambiance.Subsequently with the extremely loose particle membrane of gained between two steel plates with 100kg/cm 2Pushed 2 minutes.Under this pressure, film significantly compresses, and reduces to about 70% porosity (referring to Fig. 6) and be higher than 90% initial porosity certainly.Subsequently with TiO 2Layer heated 2 hours in 500 ℃ in air.Said film is cooled to room temperature, and through 5.0 * 10 of suitable-two (thiocyanic acids) two (2,2-bipyridine 4, the 4-dicarboxylic ester) ruthenium (II) in ethanol -4The said film of dipping made said film dyeing in 6 hours in the M solution.For forming hole gatherer coating 740, with several CuBO that drop in the ethanol 2Suspension is placed in dyed TiO 2On the film and with 800rpm spin coating 2min.Thin graphite linings is coated on dyed TiO 2/ CuBO 2On the layer, with the better electrical contact between obtaining electrode and the back of the body contacting.To have fine and close CuBO 2Thin layer (～50nm) glass plate 760 of 750 coating electric conductive oxidation indium tin (ITO) is as back of the body contact.Densification back of the body contact 750 is coated to the glass plate 760 of coating ITO through PLD.Perhaps, can deposit back of the body contact 750 through sputtering sedimentation, molecular beam epitaxy (MBE), pulsed electron beam deposition, electron beam evaporation, other physical vapor deposition technology and sol-gel/chemical deposition technique.
(AM 1.5,100mWcm in simulated solar -2Irradiation) measured energy conversion efficiency under.Figure 12 illustrates based on CuBO 2The typical light current density versus voltage curve of DSSC.Open circuit voltage (V Oc), short-circuit photocurrent density (I Sc) and fill factor, curve factor (FF) value be respectively 550mV, 1.6mA cm -2And 0.61.Gross energy conversion efficiency (η=the FF * V of solar cell Oc* I Sc/ P In) through being calculated as 0.53%.The stability of solid-state DSSC is through by computer-controlled photoelectric current the measurement of voltage characteristic being judged under (360hrs) in 15th at prolonged exposure.Carry out measurement at interval with six hours rules.During 15 days, the conversion efficiency that observes battery only reduces by 2% (referring to the illustration of Figure 12).
Through preparing penetrable dyed porous TiO 2 The CuBO of net 2 Superfines is made solid-state DSSC
Figure 13 A illustrates CuBO 2Particle 820 can not penetrate mesopore TiO too greatly effectively 2(situation of pore-size～50nm-100nm), this is the CuBO that is produced by aforesaid sol-gel technology to net 810 2Powder (the situation of particle diameter～200nm).Relatively, Figure 13 B illustrates CuBO 2Particle 830 enough little (～20nm) to penetrating dyed TiO 2The situation of net 810.Use is by the CuBO of the nano-scale of aforesaid nanometer powder instrument and the production of aforesaid method 2Particle is made DSSCs, and obtains CuBO 2Particle penetration TiO 2The device of net.Use the powder of these nano-scales, more a high proportion of p type oxide enters into mesopore TiO 2The hole in, this produces higher conversion efficiency.Carry out the detailed measurements of energy conversion efficiency by the above, and these are measured in the scope of 0.6-1.0%.(variation that it should be noted that this method is with CuBO 2Particle adds mesopore TiO 2After the structure, this structure is dyeed, rather than adding CuBO 2The said mesopore TiO of dyeing before the particle 2Structure.)
Through sol-gel technique with p type oxidate to TiO 2 Make solid-state DSSC in the hole of net
Shown in Figure 15 A, Figure 15 B and Figure 15 C, through sol-gel technique with CuBO 2Material is deposited on TiO 2In the hole of net.This technology has two variations.In first changes, with CuBO 2Material is deposited on the TiO of coating dyestuff 2In the hole of net.Figure 14 illustrates and is used to prepare CuBO 2Differential scanning calorimetry (DSC) data of citrate gel.Figure 14 illustrates gel to CuBO 2Decomposition betide～160 ℃.The decomposition temperature of ruthenium dye (Ru-535) is 250 ℃, and showing can be through this sol-gel technique with CuBO 2Be deposited on the TiO of coating dyestuff 2In the hole of net, and can not damage Ru-535.For with CuBO 2Be deposited in the hole, first step will be for containing the Cu of chelating 2+And B 3+The dilution citrate sol 920 of ion is introduced into the TiO of coating dyestuff 2In the hole of net 910 (referring to Figure 15 A).After this TiO that soaks at the about 80 ℃ colloidal sols of finding time 2Film is to convert colloidal sol into gel.This finds time to carry out through applying vacuum, avoids damaging dyestuff to keep temperature enough to be low to moderate.Repeat above-mentioned two step several times, with gel 930 filler openings (referring to Figure 15 B) with the amount of wanting.The mesopore TiO that will contain after this, gel 2Be heated to 160 ℃.Under this temperature, gel decomposition is to form CuBO 2Powder 940, this powder possibly be scattered in TiO equably 2In the net 910 (referring to Figure 15 C).Yet, the CuBO that under this temperature, forms 2Be extremely unbodied, this possibly cause adverse effect to the performance of battery.Carry out the detailed measurements of energy conversion efficiency by the above, and these are measured in the scope of 0.5-0.9%.
In changing, with CuBO based on second of the technology of sol-gel 2Material is deposited on uncoated (no dyestuff) TiO 2In the hole of web frame.Then carry out above-mentioned technology, following difference is just arranged.In this changes, can the free temperature of system not increased to 500 ℃ (because dyestuff being added into battery as yet) and improve CuBO to reach 2The purpose of degree of crystallinity.Should homodisperse TiO in the oxygen that flows 2-CuBO 2System annealing is with compensation this TiO that carbonaceous by-products was caused by gel decomposition 2-CuBO 2Any oxygen non-stoichiometry of material system.Through with TiO 2-CuBO 2System impregnated in 6-12 hour this system that dyes in the dye solution.Because these materials have the trend that becomes porous, so the CuBO in mesh 2Particle and TiO 2There are some between the wall of net at interval.Dye molecule arrives these at interval because of capillarity.Except this CuBO 2Particle diameter maybe be with beyond bigger, the structural similarity of resulting structures and Figure 15 C.There is necessary optimised several parameters, like CuBO 2Amount, amount of dye, TiO 2The aperture of net etc.Carry out the detailed measurements of energy conversion efficiency by the above, and said measurement is in the scope of 0.5-0.9%.
Can embed TiO through preparation 2 The CuBO of particle 2 The porous net is made solid-state DSSC
Through at first preparing CuBO 2Porous net and produce TiO subsequently 2The web of nano particle is made solid-state DSSC.The major part work of DSSC is passed through to make TiO 2Porous net and subsequently electrolyte being inserted in the hole is accomplished.Yet, when using solid p type hole gatherer, can put upside down the order of manufacturing step.This method is for based on CuBO 2The hole gatherer important with particularly, particle or crystal grain have the tropism that size is grown greatlyyer in said gatherer.Crystal grain/particle growth takes place with temperature through solid-state diffusion and Oswald slaking in time.Figure 16 illustrates the sketch map of this DSSC battery structure.
In Figure 16, DSSC is made up of 1010 of glass substrates with transparent conductive oxide (ITO) coating 1015.Use the method identical, will approach the CuBO of (50nm) through pulsed laser deposition (PLD) technology with such scheme 2Dense coating 1020 is deposited on the substrate 1010,1015.After this, with mesopore CuBO 2Layer 1030 is deposited on fine and close CuBO 2On the layer 1020.For this reason, through stirring some hrs with a small amount of CuBO 2Powder (average diameter～100nm) be suspended in the straight alcohol, and will be suspended in a small amount of CuBO in the straight alcohol subsequently 2The powder spread is to substrate surface.With gained ethanol/CuBO 2Powder bed is dry in ambiance, then with gained ethanol/CuBO 2Powder bed between two steel plates with 100kg/cm 2Pushed 2-5 minute.Under such pressure, CuBO 2Layer 1030 is compression significantly.Subsequently with CuBO 2Layer 1030 heats 2-5hrs down in 500 ℃ in air.For with TiO 2Nano particle 1040 inserts CuBO 2In the hole of layer 1030, with several TiO that drop in the ethanol 2Suspension is placed in dyed CuBO 2On the layer 1030 and with about 1000rpm spin coating 2min.Repeat this step several times, with TiO that will the amount of wanting 2Nano particle 1040 inserts CuBO 2In the hole of layer 1030.After this in air, under 500 ℃, anneal.Through the TiO that will therefore obtain 2And CuBO 2Web impregnated in this net of cause dye-coated in the ethanolic solution of dyestuff.In final step, through having fine and close TiO 2The transparency conductive electrode 1060 of layer 1050 is placed in assembles this DSSC on the DSSC.Be applied in the light pressure sufficient to guarantee good electrical contact that is used for compressing this DSSC.Carry out the detailed measurements of energy conversion efficiency by the above, and said measurement is in the scope of 0.6-1.0%.
Use TiO 2 -CuBO 2 " core-shell " nano particle is made solid-state DSSC
Figure 17 A and Figure 17 B illustrate TiO 2-CuB 2" core-shell " nano particle, said nano particle allow to form the new method of DSSC through special design.In conventional DSSCs, make device with the mode of dye coating between n N-type semiconductor N and hole collector layer.Yet, in some embodiments of the invention, not with dye-coated in TiO 2And CuBO 2Interface on, but with dye-coated in TiO 2-CuB 2On the surface of " core-shell " particle.
Preparation TiO 2-CuB 2" core-shell " particle.Through outer surface, said " core-shell " particle is used to make DSSCs with dyestuff 1150 sensitizations said " core-shell " particle.Synthetic two kinds of different types of " core-shell " particles: (i) TiO 21110 as core and CuBO 21120 as shell (Figure 17 A), reaches (ii) CuBO 21130 as core and TiO 21140 as shell (Figure 17 B).Has TiO in order to prepare 2" core-shell " nano particle of core is with dilution salpeter solution (pH～4) washing TiO 2Nano particle, and add a small amount of positive tetraethyl titanate (Ti (OC 2H 5) 4) only to be coated with said nano particle.After stirring one hour, the pH of this suspension is adjusted into 5-6, and is stirring simultaneously with CuO 2And B 2O 3Acid salpeter solution dropwise add this suspension.For the formation that promotes " core-shell " nano particle and for fear of solid CuBO 2Formation, keep low drop rate, and, then adjust TiO if need 2The pH of nanoparticle suspension is to change CuBO 2Form speed.Confirm to be used for obtaining the required CuO of shell average thickness that wants with experimental technique 2And B 2O 3Amount, and use transmission electron microscopy directly to measure thickness of the shell.Has CuBO in order to prepare 2" core-shell " nano particle of core is with dilution nitric acid (pH～4) washing CuBO 2Nano particle, and add enough positive tetraethyl titanates only to be coated with said nano particle.(look want particle diameter and decide, use one of said method to make CuBO 2Core.) after stirring one hour, the positive titanate that adds extra aliquot until obtain want thickness of the shell till.Wash end-product with deionized water, and characterize end-product with assessment " core-shell " form and overall size and distribution of shapes with TEM and SEM.
In order to assemble DSSC shown in Figure 180, will have thin TiO 2The transparency conductive electrode 1210 of coating 1220 impregnated in the dilution nitric acid and makes excellent sealing with this electrode surface of chemical activation and between this electrode surface and active device layer.The concentrated suspension liquid of " core-shell " particle 1230 is mixed with electron transfer dye solution in the ethanol, and on concentrated suspension liquid of " core-shell " particle 1230 that will mix and electron transfer dye solution spray drying to the said surface.With a small amount of CuO 2And B 2O 3Dilution salpeter solution spray drying on this, and will be coated with CuBO subsequently 21240 electrically conducting transparent is placed in the top to electrode 1250.Under vacuum environment in about 80 ℃ with this overall structure heating some minutes to remove solvent and with said layer annealing.Carry out the detailed measurements of energy conversion efficiency by the above, and said measurement is in the scope of 1.0-1.2%.
Use TiO 2 -CuB 2 " nanometer coupling " made solid-state DSSC
In the case, use the polymer attachment with TiO 2With CuBO 2Keep together in couples.Said " nanometer coupling " can be caught light and separated charge simultaneously.Figure 19 illustrates TiO 2-CuB 2The sketch map of " nanometer coupling ".Should " nanometer coupling " comprise a pair of TiO that keeps by polymer sept 1330 2 Particle 1310 and CuBO 2Particle 1320.Polymer sept 1330 also provides the interface between the said particle, and ionizable light absorbing dyestuff 1340 gathers on this interface.The electronics and the hole that produce in the dyestuff 1340 can be transferred to TiO respectively fast 2Particle 1310 and CuBO 2Particle 1320.
With TiO 2And CuBO 2Nano particle begins as raw material and uses the step of describing among Figure 20 to synthesize " nanometer coupling ".(look want particle diameter and decide, use one of said method to make CuBO 2Nano particle.) at first, with TiO 2Nano particle is attached to hydrophily chromatographic media post (as by BioRad, Hercules, CA provides).With this post of washing with alcohol to remove loose nano particle.After this, use the carboxyethyl phosphoric acid (CEPA) of 1M in ethanol to wash this post once more, to come the functionalized TiO that is exposed through the carboxylic acid group 2Nanoparticle surface.This post is opened to be used for slurries.1-ethyl-3-[3-dimethyl aminopropyl] carbonization imidodicarbonic diamide hydrochloride (EDAC) and N-hydroxyl sulfoacid base-succinimide (SNHS) are added into (as far as lip-deep each carboxyl of nano particle, 1 equivalent) in the slurries, and at room temperature stirred 30 minutes.Subsequently, with PEG couplant (NH 2-PEO n-NH 2) be added in these slurries and stirred overnight at room temperature.With these slurries of washing with alcohol, to remove unreacted material but keep TiO 2Nano particle.In a detached column, with CuBO 2The CuBO that the nano particle supporter combines 2Nano particle and CEPA react, to make said nano particle part functionalized through the carboxylic acid group.Said nano particle is by the water-based ethanol gradient elution, and the warp dialysis is to remove unreacted material.The coated materials that this is purified is to containing TiO 2The slurries of nano particle and EDAC, and add SNHS with together with said particle binding.This is dialysed with CEPA, EDAC and the SNHS that removes any remnants through salvage material.Via people such as Zhang " Oxidation chemistry of poly (ethylene glycol)-supported carbonylruthenium (II) and dioxoruthenium (VI) mesotetrakis (pentafluorophenyl) porphyrin "; Chemistry 12; The program of general introduction among the 3020-3031 (2006), ruthenium misfit thing through with dimethyl formamide (DMF) in the sodium hydride reaction be able to be attached to the PEG binding agent in " nanometer coupling ".Length and structure through to this sept polymer are carried out system manipulation, change the separation between the said particle and insert the amount of dye between the said particle.Through the scheme identical scheme of use, use TiO with " core-shell " particle of above-mentioned being used for 2-CuB 2" nanometer coupling " made DSSCs.Carry out the detailed measurements of energy conversion efficiency by the above, and said measurement is in the scope of 1.0-1.4%.
With Ru-535 with the instance that is fit to that acts on above-mentioned DSSCs based on the sensitizing dyestuff of ruthenium; Yet, can use other dyestuff, comprise low-cost dyestuff.Some instances of substituting dyestuff are the dyestuff based on copper and iron, for example Cu (3) 2[PF 6] or FeL 2(CN) 2In addition, having the non-aqueous solvent (like, hydrazine) of high-k can be in order to strengthen dyestuff and semi-conducting electrode (like, CuBO 2And TiO 2) adhesion.(can remove excessive tackifier through applying vacuum or at high temperature evaporating.)
With TiO 2With the instance that acts on the n type, semiconductor material that is fit among the above-mentioned SS-DSSCs.Yet, can use other material (to comprise ZnO and ZrO 2) as TiO 2Substitute.For example:, can use ZnO and ZrO forming in " core-shell " nano particle with the copper boron oxide compound 2Substitute TiO 2And forming in " nanometer coupling " with copper boron oxide compound nano particle, can use ZnO and ZrO 2Nano particle substitutes TiO 2Nano particle.
In addition, of in the early time, the p type copper boron oxide compound in the above-mentioned SS-DSSCs instance can be by other p type delafossite copper product, like CuAlO 2, CuGaO 2And CuInO 2Substitute.
In alternate embodiment of the present invention, copper boron oxide compound depositing of thin film can comprise sputtering technology, molecular beam epitaxy (MBE), pulsed electron beam deposition, electron beam evaporation, other physical vapor deposition technology and sol-gel deposition technique.Citrate sol-gel process in order to form the copper boron oxide powder can be through adjusting with synthetic copper boron oxide compound film.By the above-mentioned sol-gel solution for preparing.After refluxing, part is evaporated this solvent, and then produces viscous liquid.Subsequently, use this viscous liquid through solution deposition techniques (as, dip-coating, spraying, ink jet printing or spin coating) deposited copper boron oxide compound film.At about 50 ℃ of dry down films that deposited, and, can deposit additional coatings to realize the film of the thickness of being wanted if need.5 and 50Torr between vacuum under sintering should be through sol-gel coating of drying, to form copper boron oxide compound film between 70 and 200 ℃.After forming this copper boron oxide compound film, can sintering temperature be increased to about 300-600 ℃ (according to because the temperature limitation due to the type of substrate) with this film of closeization.
Although copper boron oxide compound material of the present invention is described to have the delafossite crystal structure, also can there be alternative crystal structure in this material, comprises hexagonal closs packing (HCP) crystal structure.
Specifically described the present invention although consult the embodiment of the invention, those skilled in the art should be easily understood that, in change and the modification that can carry out under the situation without departing from the spirit or scope of the invention on form and the details.

Claims (15)

1. solid-state dye sensitized solar cell comprises:
The p type, semiconductor material, said p type, semiconductor material has CuBO 2General composition and stoichiometry;
The n type, semiconductor material;
Dyestuff; With
A pair of electrode;
The first is optically transparent at least in the wherein said a pair of electrode, and wherein said n type, semiconductor material, said p type, semiconductor material and said dyestuff are between said a pair of electrode.
2. according to the solar cell of claim 1, wherein said n type, semiconductor material formation hole pattern and said p type, semiconductor material are in said hole.
3. according to the solar cell of claim 1, the form that wherein said n type, semiconductor material and said p type, semiconductor material are core-shell particles.
4. according to the solar cell of claim 1; Wherein said n type, semiconductor material and said p type, semiconductor material are configured to nanometer coupling particle, and said nanometer coupling particle respectively comprises p N-type semiconductor N particle, n N-type semiconductor N particle and the polymer that said p N-type semiconductor N particle and said n N-type semiconductor N particle are combined.
5. method of making solid-state dye sensitized solar cell, said method comprises:
First transparency electrode is provided;
On said first transparency electrode, form one deck, said layer comprises p type, semiconductor material and n type, semiconductor material, and said p type, semiconductor material has CuBO 2General composition and stoichiometry;
Second transparency electrode is provided; With
Said second substrate is put on said layer, and wherein said first transparency carrier is parallel with said second transparency carrier.
6. according to the method for claim 5, the said layer of wherein said formation comprises:
On said first transparency electrode, form the mesoporous layer of n N-type semiconductor N; With
Hole with the said mesoporous layer of p N-type semiconductor N nano-particles filled.
7. according to the method for claim 5, the said layer of wherein said formation comprises:
On said first transparency electrode, form the mesoporous layer of n N-type semiconductor N; With
Use sol-gel technology and heating, fill the hole of said mesoporous layer with p N-type semiconductor N powder.
8. the method for a manufactured copper boron oxide compound film on substrate, said method comprises:
Produce a bronze medal boron oxide powder through a low-temperature sol-gel technology;
Compress said copper boron oxide powder to form a target; With
In a film deposition tool, use said target on said substrate, to form said copper boron oxide compound film;
Wherein said copper boron oxide compound film comprises an optically transparent p type, semiconductor material, and said p type, semiconductor material has CuBO 2General composition and stoichiometry.
9. according to Claim 8 method, wherein said low-temperature sol-gel technology comprises:
Dissolve CuO and B respectively 2O 3And with CuO and B 2O 3Combination is to form a homogeneous solution;
Use chelating agent in said homogeneous solution chelating Cu and B to form a chelate solution;
Dilute said chelate solution to form a dilute solution;
Said dilute solution is refluxed to form a reflux solution;
Evaporate said reflux solution to form a gel; With
Burn said gel to form said copper boron oxide powder.
10. according to Claim 8 method, further comprise the said substrate of heating and with the temperature limit of said substrate to being lower than 500 degree Celsius.
11. method according to Claim 8 further is included in during the said formation, keeps the partial pressure of oxygen in the said film deposition tool.
12. a clear films transistor comprises:
Transparency carrier;
Transparent grid electrode layer on said transparency carrier;
Gate insulator layer on said grid layer;
Channel layer on said gate insulator layer, said channel layer comprise transparent p type semiconductive copper boron oxide compound; With
Source electrode on the upper surface of said channel layer and drain contact.
13., further comprise the diffused barrier layer between said gate insulator layer and said channel layer according to the transistor of claim 12.
14. a thin-film solar cells comprises:
Substrate; And
Copper boron oxide compound p layer on said substrate, said copper boron oxide compound p layer comprises optical clear p type, semiconductor material, said optical clear p type, semiconductor material has CuBO 2General composition and stoichiometry.
15. the solar cell according to claim 14 further comprises:
N type transparent conductive oxide film between said substrate and said copper boron oxide compound p layer;
Amorphous silicon absorber layer on said copper boron oxide compound p layer;
N type amorphous silicon layer on said amorphous silicon absorber layer; And
Back contact on said n type amorphous silicon layer.
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